The present invention relates to new alkoxylated alkyl substituted phenol sulfonate compounds. Further, this invention relates to surfactant compositions containing these novel compounds, to a method for preparing these new alkoxylated alkyl substituted phenol sulfonate compounds and to a method for using these compositions in enhanced oil recovery, as emulsifiers, in emulsion polymerization, as hydrotypes, in foamed drilling fluids, as dye carriers, as textile detergents, as foaming agents for concrete formulations, and as fiber lubricants.
Petroleum is naturally recovered from subterranean formations in which it has accumulated by penetrating the formations with one or more wells and pumping or permitting the petroleum to flow to the surface through these wells. Recovery of petroleum from formations is possible only if certain conditions exist in the formations. The petroleum must be present in the formation in an adequately high concentration, and there must be sufficient permeability or interconnected flow channels within the formation to permit the flow of fluid if sufficient pressure is applied to the fluid. When the formation has natural energy present in the form of underlying active water drive, or gas dissolved in the petroleum which can exert pressure to drive the petroleum to the producing well, or a high pressure gas cap above the petroleum within the formation, this natural energy may be utilized to recover petroleum. Recovery of petroleum by utilization of natural energy is referred to as primary recovery. When this natural energy source is depleted, or in those instances where the formation does not contain sufficient natural energy to support primary recovery, some form of supplement or enhanced recovery process must be applied to the formation in order to extract petroleum therefrom.
Water flooding, which involves the injection of water into the subterranean, petroliferous formation for the purpose of displacing petroleum towards the producing well, is the most economical and widely practiced supplemental recovery method. Water does not displace petroleum with high efficiency, however, since water and oil are immiscible, and also because the interfacial tension between oil and water is quite high. This inherent weakness of water flooding has led to the introduction of many additives for decreasing the interfacial tension between the injection water and the formation petroleum. For example, polyglycol ether has been used as a surface active agent or surfactant to increase the capillary displacement efficiency of an aqueous flooding medium. Other surfactants which have been proposed for oil recovery operations include alkylpyridinium, alkylsulfates, alkylarylsulfates, ethoxylated alkyl or alkylaryl sulfates, alkylsulfonates, and alkylaryl sulfonates.
While the above described surfactants may be effective in surfactant recovery operations under ideal conditions, there are problems associated with the use of these materials in some petroleum containing formations. For example, the passage of an aqueous solution containing two totally different species of surfactants dissolved therein frequently results in the selective absorption of one material more than the other, or the absorption of one of the materials at a different rate than the other. Since the optimum performance of a multi-component surfactant system is achieved only when the various surfactant species are all present in critical concentrations, this shift in concentration as a result of selective absorption of surfactant can result in there being non-optimum or even inoperative concentrations of surfactants at certain points in a formation.
Another problem which frequently degrades the performance received from surfactant flooding operations is associated with the formation temperature. Petroleum sulfonates as well as other alkyl or arylalkyl sulfonates are relatively stable at temperatures normally encountered in subterranean petroleum containing formations. However, these materials are usually not effective in the presence of high salinities and/or high formation water hardeners. Conversely, nonionic surfactants such as polyethoxylated alkyl phenols are effective for surfactant flooding in formations containing high salinity water or hard water, but these materials become insoluble at temperatures in the range of from about 100.degree. to about 125.degree. F., referred to as their cloud point. Thus, while the materials are not degraded permanently, they are removed from aqueous solution and therefore are ineffective so long as the temperature is above their cloud point.
It is widely recognized that hydrotropes are useful as additives by the detergent industry. Hydrotropes increase the solubility and the rate of dissolution of detergents in water. However, none of the hydrotrope additives currently in use by the detergent industry possesses the characteristics of increasing the solubility, the rate of dissolution as well as possessing good surfactant properties, such as low surface and interfacial tension.
Numerous attempts have been made, of course, to improve the solubility and rate of dissolution of a detergent in water by use of hydrotropes as additives. Further, a search for an hydrotrope additive that possesses the above described characteristics as well as possessing good surfactant properties has been made but such attempts have in general only met with limited success. Thus, the compounds of this invention, when added to a detergent, improve the solubility and rate of dissolution of the detergent in water. Additionally, these compounds possess good surfactant properties that allow the hydrotrope additive to increase the cleaning effect of the detergent as well as increasing the solubility and rate of dissolution of the detergent.
Various attempts have been made at inhibiting corrosion of metal surfaces and deposits thereof. This problem has a wide application in a variety of industrial settings. Various techniques have been employed in an attempt to prevent corrosion and inhibit deposition on metal surfaces. One method of preventing the corrosion and deposit has been a composition which combines a corrosion inhibiting amine and a surfactant that seems to provide increased corrosion inhibition to metal surfaces as well as possessing antifouling characteristics. While these compositions are a definite improvement over other prior art processes, the need still exists for a method of preventing corrosion of metal surfaces that still face many sectors of the manufacturing community.
The present invention overcomes the deficiency of prior art corrosion inhibitors by the addition of the novel alkoxylated alkyl substituted phenol sulfonate compounds. These compounds are soluble in kerosene and water making them excellent candidates for various industrial and manufacturing applications.
It is widely known to use various surfactants to emulsify monomers, such as styrene, vinyl chloride, vinyl acetate, acrylic and methacyrlic acid esters and others. Additionally, it is known to use surfactants to emulsify mixtures of monomers in water and in emulsions polymerized using free radical initiators such as sodium persulfate. However, the surfactants utilized in these various emulsion polymerization processes have not overcome all problems associated with these processes. For example, emulsion processes that employ organic solvents, instead of water as the solvent, still must face the additional problem of environmental pollution and meeting the increasingly stringent federal, state and local regulations with regard to pollution. Thus, a method of emulsion polymerization is needed that utilizes surfactants that have enhanced surfactant properties and can be used in a water based system in order to avoid the pollution problems of the prior art processes.
Various attempts at improving the characteristics of concrete formulation has long been sought by the industry. Due to the importance of concrete as a building material as well as its other uses, improved characteristics are essential in order to fulfill various new applications. Attainment of improved characteristics such as 1) improvement of workability and resulting reduction of water-cement ratio and the quantity of fine aggregate, 2) increase of the water-retaining force by air bubbles and resulting reduction of bleeding, and 3) improvement of pumpability are essential in the use and development of cement.
Several methods have been tried to attain these characteristics, the primary method includes the addition of highly oxidized resin acid salts, salts of protein substances, salts of alkyl benzenesulfonates and polyoxyethylene alkyl sulfates as well as various non-ionic surface active agents.
These methods, while successful in some respects, have not attained the improved properties still needed by the concrete industry. For example, the improvement of workability and reduction of water-cement ratio still persists.
Fiber finishing compositions are a necessary part of modern, high speed synthetic fiber manufacture. Virtually all operations performed on fibers following their being spun from the melt require the present of suitable fiber finishes to prevent snarling and breaking, thus enabling high fiber throughput. Generally speaking, a quality fiber finish must provide several often conflicting qualities. For example, the fiber finish must qualify for both the interaction between the fiber and the machinery on which it is processed and also the interactions among the fiber filaments themselves. This property is usually termed "lubricity" although in reality the change in the interactions caused by the fiber lubricant may sometimes result in a desirable increase in friction as well as the decrease in friction ordinarily associated with the term lubricant.
Prior art lubricants include material oils and waxes, fatty acid esters such as butyl stearate, vegetable oils and waxes, neoalcohol esters, silicones and polyoxyalkene polyethers. However, even relatively small amounts of residue that occur with these prior art lubricants can produce a resinous buildup on the heater plates at high process speeds. Thus, the requirement of a lower residue fiber lubricant suitable for high speed fiber processing is needed despite current fiber lubricants.
During the weaving of textiles, the warp threads are normally protected against breakage by application of a size. The presence of size on the warp threads interferes with finishing processes such as bleaching and dyeing and complete removal of size is highly desirable to obtain an even treatment such as even dyeing.
Various attempts at overcoming these problems have been made. For example, a process of applying a dyeing liquor or a printing paste that in addition to the dyestuffs includes non-ionic, amionic or cationic surfactants. These prior art processes, while improving the dyeing process, still has not overcome all problems associated with the dyeing process. Thus, the requirement of an improved dye carrier that lowers the amount of energy, time and additional chemicals are still needed.
As is well known, general purpose household detergents comprising a surfactant and a builder do not have sufficient power to remove oily dirt, and therefore, soiled materials washed therewith may yellow after storage for a long period of time. Heavily stained portions cannot be cleansed sufficiently by the usual washing process and, therefore, a more concentrated detergent solution is sometimes used. However, such a treatment is not preferred for general household use because of the difficulty of using same and/or it may damage the fabric or damage the shape of the clothing.
On the other hand, cleaning with solvents (dry cleaning) is suitable for removing oily dirt. However, this method has the disadvantage that water-soluble dirt and inorganic solid dirt cannot be removed. A system has been developed wherein a without detergent comprising a surfactant, a small quantity of water and a solvent is used. However, this system is not suitable for general household use, because a large quantity of a solvent is required.
U.S. Pat. No. 4,018,278 relates to an oil recovery process that utilizes a surfactant which is generally characterized as surfactant solution selected from water soluble salts of sulfonated ethoxylated alcohols and sulfonated ethoxylated alkylaryl compound and mixtures thereof. The surfactants of this reference are stable in formations whose waters contain concentrations of salt and/or divalent ions such as calcium and magnesium, as well as temperatures in excess of 120.degree. F. The surfactants are preferably utilized as the sole constituent in an aqueous solution for use in oil recovery operations, or may be used in combination with an anionic surfactant such as petroleum sulfonate, alkyl sulfonate or alkylaryl sulfonate.
U.S. Pat. No. 2,828,334 discloses oxypropylated, oxyethylated, and oxybutylated derivatives of certain substituted phenol sulfonic acids and their salts as well as a method of making these compounds.
While the art has provided alkoxylated alkyl substituted phenol sulfonate compounds having a wide variety of properties, the need still exists for surfactant compounds having different and/or enhanced surfactant properties. For example, an important use of surfactants is in the enhanced hydrocarbon recovery operations. Further, many petroleum sulfonates are widely used as hydrotypes, dye carriers, foamed drilling fluids, textile detergents, fiber lubricants, in emulsion polymerization, and corrosion inhibitors. As is well known to those skilled in the art, petroleum sulfonates have recently emerged as the principal surfactants associated with enhanced oil recovery. However, these petroleum sulfonates when utilized in enhanced oil recovery operations must possess increased stability where the formation has temperatures in excess of 125.degree. F. and has a high brine content.
Accordingly, it is one object of the present invention to provide novel alkoxylated alkyl substituted phenol sulfonate compounds.
Another object of this invention is to provide novel alkoxylated alkyl substituted phenol sulfonate compounds having enhanced surfactant properties.
A further object of this invention herein is to provide a new method in the preparation of these novel alkoxylated alkyl substituted phenol sulfonate compounds.
Still another object of this invention is to provide surfactant compositions containing these novel alkoxylated alkyl substituted phenol sulfonate compounds.
A still further object of this invention is to provide a method of using these novel surfactant composition in enhanced oil recovery operations.
Yet still another object of this invention is to provide a method of improving the solubility and rate of dissolution of detergents by the addition of these novel compounds.
A further object of this invention is to provide a method of improving corrosion inhibitors by the addition of these novel compounds.
A further object is to provide a method of improving emulsion polymerization by the addition of these novel compounds.
A still further object is to provide a method of improving concrete formation by the addition of these novel compounds.
Still another object of this invention is to provide a method of improving foamed drilling fluids by the addition of the novel compounds.
A still further object is to provide a method of improving dye carrier in textile by the addition of the novel compounds of this invention.
Yet another object of this invention is to provide a method of improving textile detergents by the addition of these compounds.
Still another object is to provide a method of improving fiber lubricants by the addition of these novel compounds.
These and other objects are achieved by alkoxylating alkyl substituted phenol sulfonates of the present invention. Briefly, this invention relates to novel alkoxylated alkyl phenol sulfonate compounds, novel surfactant compositions containing these novel compounds, the preparation of these surfactant compounds and compositions as well as the use of these surfactant compounds in enhanced oil recovery operations, as emulsifiers, in emulsion polymerization, as hydrotypes, in foamed drilling fluids, as dye carriers, as textile detergents, as foaming agents for concrete formation and as fiber lubricants. These compositions exhibit high thermal stability, low surface tension and low interfacial tension. These properties are contrary to the results expected from this type of alkoxylated alkyl substituted phenol sulfonate compositions.
In particular, this invention relates to compounds having the structural formula ##STR2## wherein R.sub.1 is an alkyl group having about 8 to about 24 carbon atoms, R.sub.2 is an alkylene oxide having about 2 to about 4 carbon atoms, M.sup.+ is selected from the group consisting of Na, K, Li, Ca, Ba, Sr, Mg, Zn and amine salts thereof, and n is an integer from 1 to about 4 with the provisio that when R.sub.2 is ethylene oxide, then R.sub.1 is an alkyl up having at least 3 n carbon atoms, when R.sub.2 is propylene oxide, then R.sub.1 is an alkyl group having at least n carbon atoms, and when R.sub.2 is butylene oxide, then R.sub.1 is an alkyl group having at least 0.75 n carbon atoms.
In another embodiment, this invention relates to surfactant compositions which include at least 90% of an aqueous medium and not more than 10% of a compound having the structural formula ##STR3## wherein R.sub.1 is an alkyl group having about 8 to about 24 carbon atoms, M.sup.+ is selected from the group consisting of Na, K, Li, Ca, Ba, Sr, Mg, Zn and amine salts thereof, and n is an integer from 1 to about 4, with the provisio that when R.sub.2 is ethylene oxide, then R.sub.1 is an alkyl group having at least 3 n carbon atoms, when R.sub.2 is an alkyl group having at least n carbon atoms, and when R.sub.2 is butylene oxide then R.sub.1 is an alkyl group having at least 0.75 carbon atoms.
In still another embodiment, the compounds of this invention are prepared by a process comprising compounds having the structural formula ##STR4## wherein R.sub.1 is an alkyl group having about 8 to about 24 carbon atoms, R.sub.2 is an alkylene oxide having about 2 to about 4 carbon atoms, M.sup.+ is selected from the group consisting of Na, K, Li, Ca, Ba, Sr, Mg, Zn and amine salts thereof, and n is a whole number from about 1 to about 4, with the provisio that when R.sub.2 is ethylene oxide, then R.sub.1 is an alkyl group having at least 3 n carbon atoms, when R.sub.2 is an alkyl group having at least n carbon atoms, and when R.sub.2 is butylene oxide then R.sub.1 is an alkyl group having at least 0.75 carbon atoms; which comprises the steps of (a) mixing a phenol having the formula ##STR5## wherein R.sub.1 has the same meaning as defined for formula (1), with a sulfonating agent to produce a sulfonic acid intermediate having the SO3H group in ortho position with respect to the OH group of said phenol material;
(b) adding a solvent to said acid intermediate;
(c) neutralizing said acid intermediate with a base to produce a sulfonate compound having the formula ##STR6## wherein R.sub.1 and M.sup.+ have the same meaning defined above following Formula (1); and
(d) reacting said sulfonate with an alkylene oxide to produce the compound of Formula (1).
A still further embodiment of this invention relates to a method for hydrocarbon recovery from a subterranean formation comprising:
(a) injecting into at least one injection well a surfactant composition comprising at least 90% aqueous and not more than 10% of a compound having the structural formula ##STR7## wherein R.sub.1 is an alkyl group having about 8 to about 24 carbon atoms, R.sub.2 is an alkylene oxide having about 2 to about 4 carbon atoms, M.sup.+ is selected from the group consisting of Na, K, Li, Ca, Ba, Sr, Mg, Zn and amine salts thereof, and n is an integer from 1 to about 4, with the provisio that when R.sub.2 is ethylene oxide, then R.sub.1 is an alkyl group having at least 3 n carbon atoms, when R.sub.2 is an alkyl group having at least n carbon atoms, and when R.sub.2 is butylene oxide then R.sub.1 is an alkyl group having at least 0.75 n carbon atoms.
(b) causing said injected surfactant composition to move from the injection well towards one or more production wells displacing hydrocarbon present in said formation; and
(c) recovering displaced hydrocarbon from at least one of said production wells.
Yet in another embodiment, this invention relates to a method of improving the solubility and rate of dissolution of detergents which comprises adding to said detergents about 1% to about 10% weight of a compound having the general formula ##STR8## wherein R.sub.1 is an alkyl group having about 8 to about 24 carbon atoms, R.sub.2 is an alkylene oxide having about 2 to about 4 carbon atoms, M.sup.+ is selected from the group consisting of Na, K, Li, Ca, Ba, Sr, Mg, Zn and amine salts thereof, and n is an integer from 1 to about 4, with the provisio that when R.sub.2 is ethylene oxide, then R.sub.1 is an alkyl group having at least 3 n carbon atoms, when R.sub.2 is propylene oxide, then R.sub.1 is an alkyl group having at least n carbon atoms, and when R.sub.2 is butylene oxide, then R.sub.1 is an alkyl group having at least 0.75 n carbon atoms.
Still another embodiment of this invention relates to a method of improving the effectiveness of corrosion inhibitors which comprises adding to said inhibitor about 1% to 10% of a compound having the general formula ##STR9## wherein R.sub.1 is an alkyl group having about 8 to about 24 carbon atoms, R.sub.2 is an alkylene oxide having about 2 to about 4 carbon atoms, M.sup.+ is selected from the group consisting of Na, K, Li, Ca, Ba, Sr, Mg, Zn and amine salts thereof, and n is an integer from 1 to about 4, with the provisio that when R.sub.2 is ethylene oxide, then R.sub.1 is an alkyl group having at least 3 n carbon atoms, when R.sub.2 is propylene oxide, then R.sub.1 is an alkyl group having at least n carbon atoms, and when R.sub.2 is butylene oxide, then R.sub.1 is an alkyl group having at least 0.75 n carbon atoms.
A further embodiment of this invention relates to improving the efficiency of emulsion polymerization which comprises adding to said polymerization about 1% to about 10% weight of a compound of the formula ##STR10## wherein R.sub.1 is an alkyl group having about 8 to about 24 carbon atoms, R.sub.2 is an alkylene oxide having about 2 to about 4 carbon atoms, M.sup.+ is selected from the group consisting of Na, K, Li, Ca, Ba, Sr, Mg, Zn and amine salts thereof, and n is an integer from 1 to about 4, with the provisio that when R.sub.2 is ethylene oxide, then R.sub.1 is an alkyl group having at least 3 n carbon atoms, when R.sub.2 is propylene oxide, then R.sub.1 is an alkyl group having at least n carbon atoms, and when R.sub.2 is butylene oxide, then R.sub.1 is an alkyl group having at least 0.75 n carbon atoms.
Another embodiment of this invention relates to a method of improving concrete formation which comprises adding to about 1% to about 10% of a foaming agent of the formula, ##STR11## wherein R.sub.1 is an alkyl group having about 8 to about 24 carbon atoms, R.sub.2 is an alkylene oxide having about 2 to about 4 carbon atoms, M.sup.+ is selected from the group consisting of Na, K, Li, Ca, Ba, Sr, Mg, Zn and amine salts thereof, and n is an integer from 1 to about 4, with the provisio that when R.sub.2 is ethylene oxide, then R.sub.1 is an alkyl group having at least 3 n carbon atoms, when R.sub.2 is propylene oxide, then R.sub.1 is an alkyl group having at least n carbon atoms, and when R.sub.2 is butylene oxide, then R.sub.1 is an alkyl group having at least 0.75 n carbon atoms.
Still a further embodiment of this invention relates to a method of improving drilling fluids which comprises adding to a foaming agent about 1% to about 10% by weight of a compound having the general formula, ##STR12## wherein R.sub.1 is an alkyl group having about 8 to about 24 carbon atoms, R.sub.2 is an alkylene oxide having about 2 to about 4 carbon atoms, M.sup.+ is selected from the group consisting of Na, K, Li, Ca, Ba, Sr, Mg, Zn and amine salts thereof, and n is an integer from 1 to about 4, with the provisio that when R.sub.2 is ethylene oxide, then R.sub.1 is an alkyl group having at least 3 n carbon atoms, when R.sub.2 is propylene oxide, then R.sub.1 is an alkyl group having at least n carbon atoms, and when R.sub.2 is butylene oxide, then R.sub.1 is an alkyl group having at least 0.75 n carbon atoms.
Still in another embodiment, this invention relates to a method of preparing improved dye carriers in textiles which comprises adding to the carrier about 1% to about 10% weight of a compound of the formula ##STR13## wherein R.sub.1 is an alkyl group having about 8 to about 24 carbon atoms, R.sub.2 is an alkylene oxide having about 2 to about 4 carbon atoms, M.sup.+ is selected from the group consisting of Na, K, Li, Ca, Ba, Sr, Mg, Zn and amine salts thereof, and n is an integer from 1 to about 4, with the provisio that when R.sub.2 is ethylene oxide, then R.sub.1 is an alkyl group having at least 3 n carbon atoms, when R.sub.2 is propylene oxide, then R.sub.1 is an alkyl group having at least n carbon atoms, and when R.sub.2 is butylene oxide, then R.sub.1 is an alkyl group having at least 0.75 n carbon atoms.
Yet another embodiment of this invention relates to a method of improving textile detergents which comprises adding to said detergent about 1% to about 10% weight of a compound ##STR14## wherein R.sub.1 is an alkyl group having about 8 to about 24 carbon atoms, R.sub.2 is an alkylene oxide having about 2 to about 4 carbon atoms, M.sup.+ is selected from the group consisting of Na, K, Li, Ca, Ba, Sr, Mg, Zn and amine salts thereof, and n is an integer from 1 to about 4, with the provisio that when R.sub.2 is ethylene oxide, then R.sub.1 is an alkyl group having at least 3 n carbon atoms, when R.sub.2 is propylene oxide, then R.sub.1 is an alkyl group having at least n carbon atoms, and when R.sub.2 is butylene oxide, then R.sub.1 is an alkyl group having at least 0.75 n carbon atoms.
Yet a still further embodiment of this invention relates to a method of improving fiber lubricants which comprises adding to said lubricants about 1% to 10% weight of a compound having the general formula ##STR15## wherein R.sub.1 is an alkyl group having about 8 to about 24 carbon atoms, R.sub.2 is an alkylene oxide having about 2 to about 4 carbon atoms, M.sup.+ is selected from the group consisting of Na, K, Li, Ca, Ba, Sr, Mg, Zn and amine salts thereof, and n is an integer from 1 to about 4, with the provisio that when R.sub.2 is ethylene oxide, then R.sub.1 is an alkyl group having at least 3 n carbon atoms, when R.sub.2 is propylene oxide, then R.sub.1 is an alkyl group having at least n carbon atoms, and when R.sub.2 is butylene oxide, then R.sub.1 is an alkyl group having at least 0.75 n carbon atoms.